Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1646—Characteristics of the product obtained
  • C23C18/165—Multilayered product
  • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
  • C23C18/2073—Multistep pretreatment
  • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/02—Electroplating of selected surface areas
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/02—Electroplating of selected surface areas
  • C25D5/022—Electroplating of selected surface areas using masking means
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/10—Electroplating with more than one layer of the same or of different metals
  • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
  • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers

Definitions

• the present invention relates to a multilayer body comprising a carrier layer made of a thermoplastic polycarbonate molding compound and a metal layer, a lighting or display unit comprising the multilayer body and a light source, a method for producing the multilayer body and the use of a thermoplastic polycarbonate molding compound as the carrier layer of such a multilayer body .
• Decorative ambient lighting elements or backlit functional/display elements are increasingly being used in automobile interiors as well as in automobile body applications.
• a market trend is to switch on/display the lighting or the display of functions only when necessary, e.g. in order to differentiate the appearance of such elements from day to night or to intensify the perception of space in the automobile interior through such ambient dynamic lighting. to enable the mapping of information according to needs and situations.
• These lighting or functional elements are, for example, (partially) translucent trim strips, decorative panels, trim panels, steering wheel covers, consoles, handles and instrument panel supports or controls with which various functions of the vehicle can be operated, such as start/stop buttons as well as controls for vehicle lighting or climate control or display elements that can be used to display information when required.
• Such components or components are generally made from technical thermoplastics, since these allow a high level of component individuality and functional integration in forming processes that are simple and cost-effective on a large scale, in particular injection molding.
• thermoplastic base body can be applied to the thermoplastic base body using different methods, for example by metal vapor deposition, back-injection of metal foils or electroplating.
• galvanization has proven itself in industry as a process for applying metal layers to plastic substrates when the aim is to create a component that is mechanically resistant to abrasion or corrosion and with good adhesion of the metal layer to the plastic base substrate, as is the case, for example, in automotive applications indoors and outdoors case is.
• openings are also referred to below as recesses or openings.
• the cutouts can, for example, have the shape of symbols, patterns, holes, lines or characters. It is also possible that these are point-shaped recesses that are arranged in the form of symbols, patterns, holes, lines or characters.
• the plastic base support in order to achieve a transilluminable component or component, the plastic base support must also be transilluminable in its typical thickness for the respective component, i.e. have good light transmission.
• the aim is usually for the carrier layer to be able to be illuminated using a light source with visible light (i.e. light in the wavelength range from 380 to 780 nm).
• the plastic base support For an appealing visual impression, it is often desirable for the plastic base support to scatter the light from a point-shaped light source, for example an LED, at least to a certain extent, thus creating a diffuse illumination image of the illuminated component. Otherwise, the light source would be visible to the viewer and/or the desired visual effect when switching on the light source would only be limited to a small area of the multi-layer body.
• a point-shaped light source for example an LED
• the carrier layer In order to achieve such a diffuse light impression of a surface of the multilayer body irradiated by a point-shaped light source, it is necessary that the carrier layer, on the one hand, has the highest possible transmission of the irradiated visible light and, on the other hand, the highest possible light diffusivity caused by light scattering, that is, the highest possible half-value angle of the light transmitted by a point-shaped light source resulting in a cone of light after passing through the carrier layer. The higher this half-value angle is, the more spatially homogeneous is the perceived illumination intensity of the light emanating from a point light source after it has passed through the carrier layer.
• the carrier layer can therefore also illuminate larger areas with point-shaped light sources with spatially largely homogeneous light intensity.
• the transmission and light diffusivity (half-value angle) of a material cannot be adjusted independently of one another and are usually opposite to each other. Optimizing light diffusivity by modifying the material, for example by changing its composition, usually results in decreasing transmission. Both variables are particularly dependent on the thickness of the material layer being illuminated, with the transmission decreasing and the light diffusivity of a translucent material increasing as the layer thickness increases.
• DE202013009793 U1 discloses a galvanically decorated component with a symbol or structure introduced into the surface in a translucent manner, in which the component is made from a galvanizable plastic using an injection molding process and the symbol is applied from a non-galvanizable, galvanically stable paint system or the symbol is printed on the component. After the electroplating process has been completed, the component can be illuminated through the uncoated, metal-free back of the component using a suitable light source and the symbolism becomes visible.
• a similar approach is used in DE102010053165 A1 described.
• a method for producing, in particular, galvanized plastic components with haptic and optical interruption structures is disclosed, in which island structures made of galvano-stable paint are applied to a galvanizable plastic component and the subsequent galvanization of the components takes place in the uncoated areas, so that only the islands in the surrounding structures are uncoated remain and the structures around the islands are coated.
• DE10208674A1 discloses a method for producing galvanically coated elements with backlightable symbols in which the initially formed first metal layer is partially removed and a symbol is exposed before the galvanic coating is completed on the first metal layer in a final step and the exposed symbol is left out of the galvanization becomes.
• the application reveals that particularly good results are achieved if the base body is made of ABS (acrylonitrile butadiene styrene) or ABS/PC (acrylonitrile butadiene styrene/polycarbonate).
• the first metal layer can be removed by etching, especially when using copper. When using nickel with a smaller layer thickness, removal can also be done using laser ablation.
• WO2017063768A1 discloses a metallized plastic component with a translucent structure in day and night design and a method for producing the plastic component.
• the metallized plastic component comprises a base body made of at least one translucent plastic, onto which a metal layer is applied, into which at least one translucent structure in the form of a dot matrix is introduced. It is disclosed that the plastic blank preferably consists at least partially of polyamide, ABS or ABS/polycarbonate blend.
• DE10320237A1 discloses a method for producing transilluminable, electroplated thermoplastic parts and transilluminable thermoplastic parts with an electroplated surface, comprising the following process steps: a thermoplastic part made of a transparent, amorphous plastic is coated with an opaque layer made of an electroplateable plastic; The galvanizable plastic is removed in the area of the symbols using a burning laser beam; An electroplating layer is applied to the galvanizable plastic. It is disclosed that particularly effective electroplating is achieved with acrylonitrile-butadiene-styrene copolymer (ABS) as an electroplateable plastic.
• ABS acrylonitrile-butadiene-styrene copolymer
• thermoplastic processability melt flowability
• high material ductility especially at low temperatures
• high heat resistance high heat resistance
• Thermoplastics that are suitable for such applications and are therefore established in such fields of application such as polycarbonate, acrylonitrile-butadiene-styrene terpolymers (ABS) and blends made from these two thermoplastics, either have poor electroplating behavior and sometimes also poor light diffusivity and/or are combined with them only insufficient metal-plastic composite adhesion is achieved in established electroplating processes, which applies to transparent polycarbonate or polycarbonate compounds provided with scattering additives, or they show good electroplating behavior but insufficient light transmission, which applies to ABS plastics previously used in this field of application and ABS/PC or PC/ABS blends apply.
• ABS acrylonitrile-butadiene-styrene terpolymers
• thermoplastically processable material having the general application technology Meets the requirements that the automotive industry places on materials for the production of components for indoor and outdoor use. Furthermore, it was desirable to provide a method for producing such a multilayer body in which the decorative metal layer is applied to the base support made of a thermoplastically processable material via an electrochemical deposition process that is industrially established in plastic electroplating, thereby achieving stable bonding.
• the carrier material on the one hand, have a combination of improved transmission for light in the visible wavelength range and high light diffusivity, i.e. a large half-value angle and good behavior in an industrially established plastic electroplating process and, on the other hand, good thermoplastic processability (melt flowability), high material ductility in particular low temperatures and high heat resistance.
• the carrier layer (I) is also referred to synonymously as a plastic carrier or plastic carrier layer.
• the molding composition of the carrier layer (I) contains less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.2% by weight of components other than component B). rubber-based graft polymers. Most preferably, the molding composition does not contain any rubber-based graft polymers other than component B).
• the molding composition of the carrier layer (I) has a rubber content in the range from 2.0 to 6% by weight, more preferably in the range from 2.5 to 5% by weight, even more preferably in the range from 2.6 to 4 .1% by weight, most preferably in the range 2.7 to 3.3% by weight.
• the carrier layer (I) consists of a thermoplastic molding material which contains at least 80% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, most preferably at least 100% by weight.
• % consists of components A, B and C.
• the multilayer body is suitable for being illuminated with visible light using a light source, that is to say the multilayer body can be illuminated.
• the light source is arranged so that the light first hits the carrier layer (I) and exits through the recesses in the metal layer (II).
• the light source is preferably an LED light source.
• Translucent means that when the light source is switched on, the visual impression on the side facing away from the light source, i.e. the visible side of the component or component in the installed state, changes.
• the multilayer body has a transmittance of at least 10%, more preferably at least 25%, even more preferably at least 40, at least in partial areas, ie at the recesses, in its actual thickness at at least one wavelength in the wavelength range of the spectrum from 380 to 780 nm % and most preferably of at least 45%, whereby the Transmittance is determined from the transmission spectrum, which is measured according to the specifications in DIN/ISO 13468-2 in the 2006 version.
• a further subject of the invention is the use of a molding compound consisting of the above-mentioned components A, B and C and the further stated features as a carrier layer (I) in a multi-layer body as described above.
• a further object of the invention is a lighting or display unit comprising the multilayer body as stated above and a light source which emits light with at least one wavelength in the wavelength range of the spectrum from 380 to 780 nm, the light source being arranged in such a way that the carrier layer of the The light emitted by the light source is irradiated.
• both the visible side and the side of the multilayer body facing away from the visible side are electrochemically exposed to a metal layer in method step (3)
• the by at least one of the optional method steps (2), (3b) and (4) in both At least one recesses introduced on the sides of the multilayer body are preferably realized in directly opposite areas of the carrier layer (I).
• the “visible side” of the multi-layer body is understood to be the side that is visible in the final application of the multi-layer body, that is, in its installation situation, in the intended function of the multi-layer body. If the multilayer body is part of a lighting or display unit in which the multilayer body is illuminated by a light source, the visible side is the side of the multilayer body facing away from the light source in the lighting or display unit.
• the multi-layer body is provided with a metal layer.
• Aromatic polycarbonates and/or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be produced using processes known from the literature (for the production of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE -A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the production of aromatic polyester carbonates, e.g. DE-A 3 007 934) .
• Aromatic polycarbonates are produced e.g. B.
• diphenols by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, according to the phase interface process, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols. It is also possible to produce them using a melt polymerization process by reacting diphenols with, for example, diphenyl carbonate.
• Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis(hydroxyphenyl)-C 1 -C 5 alkanes, bis(hydroxyphenyl)-C 5 -C 6 -cycloalkanes, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) -sulfoxides, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones and ⁇ , ⁇ ,-bis-(hydroxyphenyl)-diisopropyl-benzenes and their core-brominated and/or core-chlorinated derivatives.
• diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)cyclohexane, 1,1-bis- (4-hydroxyphenyl)-3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis(3-chloro-4-hydroxyphenyl) -propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. Particularly preferred is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol-A).
• the diphenols can be used individually or as any mixture.
• the diphenols are known from the literature or can be obtained using processes known from the literature.
• Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4-[2-(2,4,4 -Trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5- Dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol.
• the amount of to be used Chain terminators are generally between 0.5 mol% and 10 mol%, based on the
• thermoplastic, aromatic polycarbonates have average molecular weights (weight average M w ) of preferably 20,000 to 40,000 g/mol, more preferably 24,000 to 32,000 g/mol, particularly preferably 26,000 to 30,000 g/mol, measured by GPC (gel permeation chromatography) calibrated against bisphenol A -Polycarbonate standards using dichloromethane as eluent, calibration with linear polycarbonates (from bisphenol A and phosgene) with known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, calibration according to method 2301-0257502-09D (from 2009 in German) of Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane.
• the preferred ranges achieve a particularly advantageous balance of mechanical and rheological properties in the compositions according to the invention.
• thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three and more phenolic groups.
• Both homopolycarbonates and copolycarbonates are suitable.
• copolycarbonates according to the invention according to component A 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, of polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known ( US 3,419,634 ) and can be produced using processes known from the literature. Also suitable are copolycarbonates containing polydiorganosiloxane; The production of polydiorganosiloxane-containing copolycarbonates is, for example, in DE-A 3 334 782 described.
• Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
• Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred.
• a carbonic acid halide preferably phosgene
• phosgene is also used as a bifunctional acid derivative.
• chain terminators for the production of the aromatic polyester carbonates include their chlorocarbonate esters and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C 1 to C 22 alkyl groups or by halogen atoms, as well as aliphatic C 2 to C 22 monocarboxylic acid chlorides into consideration.
• the amount of chain terminators is 0.1 to 10 mol%, based on moles of diphenol in the case of phenolic chain terminators and on moles of dicarboxylic dichloride in the case of monocarboxylic acid chloride chain terminators.
• aromatic polyester carbonates When producing aromatic polyester carbonates, one or more aromatic hydroxycarboxylic acids can also be used.
• the aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934 ), with linear polyester carbonates being preferred.
• branching agents which can be used are tri- or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 up to 1.0 mol% (based on dicarboxylic acid dichlorides used) or tri- or polyfunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4, 6-Dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)- e
• Phenolic branching agents can be presented with the diphenols; Acid chloride branching agents can be entered together with the acid dichlorides.
• the proportion of carbonate structural units can vary as desired.
• the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
• Both the ester and the carbonate portion of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.
• thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture.
• Linear polycarbonate based exclusively on bisphenol A is preferably used as component A.
• the glass transition temperature T g is determined for all components using dynamic differential calorimetry (DSC) according to DIN EN 61006 (version from 1994) at a heating rate of 10 K/min with determination of the Tg as the midpoint temperature (tangent method ) determined.
• DSC dynamic differential calorimetry
• the rubber-modified vinyl (co)polymers according to component B have a melt flow rate (MVR), measured according to ISO 1133 (version from 2012) at 220 ° C with a stamp load of 10 kg, of preferably 2 to 20 ml / 10 min, particularly preferably 3 to 15 ml/10min, especially 4 to 8 ml/10min. If mixtures of several rubber-modified vinyl (co)polymers are used as component B, the preferred MVR ranges apply to the average of the MVR of the individual components weighted based on the mass proportions of the components in the mixture.
• MVR melt flow rate
• the rubber-free vinyl (co)polymer (ii) can be dissolved out using suitable solvents such as acetone.
• the size of the disperse phase (i) in the rubber-modified vinyl (co)polymers B produced in this way is adjusted via the conditions of the reaction, such as temperature and the resulting viscosity of the polymer as well as shear, for example by stirring.
• the average particle size D50 is the diameter above and below which 50% by weight of the particles lie. Unless expressly described otherwise in the present invention, it is measured for all components using ultracentrifuge measurement ( W. Scholtan, H. Lange, Colloid, Z. and Z. Polymere 250 (1972), 782-796 ) certainly.
• the monomers B.1 are a mixture of 22 to 26 parts by weight of acrylonitrile and 74 to 78 parts by weight of styrene, which optionally contains up to 10 parts by weight, particularly preferably up to May contain 5 parts by weight of n-butyl acrylate or methyl methacrylate, the sum of the parts by weight of styrene and acrylonitrile being 100 parts by weight.
• B.1 is particularly preferably free of B.1.3, with the preferred ranges mentioned above applying to B.1.1 and B.1.2.
• Preferred grafting bases B.2 are diene rubbers containing butadiene, or mixtures of diene rubbers containing butadiene or copolymers of diene rubbers containing butadiene or mixtures thereof with other copolymerizable monomers (e.g. according to B.1.1 and B.1.2).
• B.2 is styrene-butadiene block copolymer rubber.
• Component B preferably has a polybutadiene content of 5 to 18% by weight, more preferably 7 to 15% by weight, in particular 8 to 13% by weight.
• the vinyl (co)polymer (ii) which is not chemically bonded to the rubber base(s) B.2 and is not enclosed in the rubber particles can, as explained above, arise during the polymerization of the graft polymers B due to manufacturing reasons. It is also possible that a part of this vinyl (co)polymer (ii) which is not chemically bound to the rubber base(s) B.2 and is not included in the rubber particles is contained in the rubber-modified vinyl (co)polymer according to component B due to manufacturing reasons during its production Bulk polymerization process is created and another part is polymerized separately and added to component B as a component of component B.
• the proportion of vinyl (co)polymer (ii), regardless of its origin, measured as in Acetone soluble fraction in component B, based on component B, is preferably at least 50% by weight, particularly preferably at least 60% by weight, more preferably at least 70% by weight.
• this vinyl (co)polymer (ii) has a weight-average molecular weight M w of 70 to 250 kg/mol, preferably of 130 to 200 kg/mol, in particular of 150 to 180 kg/mol. mol on.
• the weight-average molecular weight M w of the vinyl (co)polymer (ii) in component B is measured by gel permeation chromatography (GPC) in tetrahydrofuran against polystyrene as a standard.
• Component B is preferably free of alkali, alkaline earth, ammonium or phosphonium salts of saturated fatty acids with 8 to 22 carbon atoms, resin acids, alkyl and alkylaryl sulfonic acids and fatty alcohol sulfates.
• Component B preferably contains less than 100 ppm, particularly preferably less than 50 ppm, most preferably less than 20 ppm ions of alkali metals and alkaline earth metals.
• Rubber-modified vinyl (co)polymers suitable as component B are, for example, Magnum TM 3404, Magnum TM 3504 and Magnum TM 3904 from Trinseo SA (Luxembourg).
• One or more representatives selected from the group consisting of polymer additives and polymer blend partners can optionally be included as component C.
• the polymer additives or polymeric blend partners are preferably selected from the group consisting of lubricants and mold release agents, stabilizers, colorants, compatibilizers, other impact modifiers different from component B, other polymeric components different from components A and B (for example functional blend partners or graft polymers with a core shell structure produced using the emulsion polymerization process) as well as fillers and reinforcing materials.
• component C does not contain any fillers or reinforcing materials. More preferably, no colorants are included. None are further preferred contain polymer blend partners. More preferably, no polymeric components are included. In a particularly preferred embodiment, neither fillers or reinforcing materials, colorants nor polymeric blend partners are included. Most preferably, neither fillers or reinforcing materials, colorants nor polymeric components are included.
• At least one polymer additive selected from the group consisting of lubricants and mold release agents and stabilizers is used as component C.
• At least one representative selected from the group consisting of sterically hindered phenols, organic phosphites, and organic or inorganic Brönstedt acids is used as the stabilizer.
• At least one representative selected from the group consisting of sterically hindered phenols, organic phosphites, and organic or inorganic Brönstedt acids is used as the stabilizer.
• fatty acid esters particularly preferably fatty acid esters of pentaerythritol or glycerol, are used as lubricants and mold release agents.
• At least one polymer additive is selected as component C from the group consisting of C8-C22 fatty acid esters of pentaerythritol, C8-C22 fatty acid esters of glycerol, tris (2,4-di-tert-butyl-phenyl) - phosphite, 2,6-di-tert-butyl-4-(octadecanoxycarbonylethyl)phenol, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyldiphosphonite, bis(2,4-di-tert-butylphenyl). )-pentaerythritol diphosphite and triethylene glycol bis [3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].
• component C does not contain any rubber-modified vinyl (co)polymer produced by emulsion polymerization.
• Thermoplastic molding compounds are produced from components A, B and C according to the invention.
• thermoplastic molding compositions according to the invention can be produced, for example, by mixing the respective components of the compositions in a known manner and at temperatures of preferably 200 ° C to 320 ° C, particularly preferably at 240 to 300 ° C, very particularly preferably at 260 ° C to 290°C in common units such as For example, internal kneaders, extruders and twin-screw screws are melt-compounded and melt-extruded.
• molding compound is therefore understood to mean the product that is obtained when the components of the composition are melt-compounded and melt-extruded.
• the individual components of the compositions can be mixed in a known manner both successively and simultaneously, both at about 20 ° C (room temperature) and at a higher temperature. This means that, for example, some of the components can be metered via the main intake of an extruder and the remaining components can be fed in via a side extruder later in the compounding process.
• the metal layer (II) is a preferably multi-layer metal layer, which is preferably applied in an electroplating process.
• the metal layer has at least one recess.
• the at least one recess can, for example, have the shape of a symbol, a pattern, a hole, a line or a character. It is also possible that these are point-shaped recesses that are arranged in the form of at least one symbol, a pattern, a hole, a line or a character.
• the multi-layer metal layer preferably consists of at least three, more preferably at least four metal layers that can be differentiated microscopically and/or chemically-analytically.
• the thickness of the preferably multilayer metal layer is 5 to 200 ⁇ m, preferably 10 to 60 ⁇ m, particularly preferably 30 to 50 ⁇ m.
• the necessary thicknesses of the individual metal layers and thus the thickness of the entire metal layer in the multilayer body according to the invention result from the requirements for the mechanical properties, resistance to environmental influences, heat resistance and other necessary properties of the component.
• the copper metal layer preferably has a thickness of 10 to 50 ⁇ m, particularly preferably 15 to 30 ⁇ m, very particularly preferably 20 to 30 ⁇ m.
• the nickel metal layer following the carrier layer (I) of the copper layer is at most half as thick as the underlying copper metal layer.
• the uppermost metal layer made of a metal with a high resistance to environmental influences preferably made of chromium, preferably has a thickness of 100 nm to 3 ⁇ m, particularly preferably of 200 nm to 1.5 ⁇ m.
• this usually and preferably has a thickness of 500 nm to 5 ⁇ m, particularly preferably 1 ⁇ m to 2 ⁇ m.
• the metal layer can be coated with a coating agent on the side facing away from the carrier layer.
• a coating is usually intended to provide mechanical protection against abrasion and scratches and/or protection against the effects of weather, ie, rain, temperature and UV radiation.
• a specific surface feel or appearance can also be achieved with a coating, Suitable coatings are, for example, thermally curing coating systems based on a polysiloxane lacquer, which can be either single-layer or multi-layer (with a primer layer between the substrate and the polysiloxane top lacquer that merely promotes adhesion).
• UV-curing coating systems for example based on acrylate, urethane acrylate or acrylic silane, which optionally contain fillers to improve scratch resistance, can also be used.
• the carrier layer (I) is formed from a thermoplastic composition as described above, preferably using an extrusion, blow molding, thermoforming or injection molding process, particularly preferably an injection molding process, for shaping in the production of this carrier .
• the carrier layer (I) is electroplated in an electroplating process established for acrylonitrile-butadiene-styrene (ABS) copolymers and their blends with polycarbonate.
• ABS acrylonitrile-butadiene-styrene
• the process parameters in process step (1) should preferably be chosen so that the carrier component used in the galvanizing process is as stress-free as possible.
• the specific conditions result from the tool geometry and the tool gate. Specific injection pressures of no more than 600 bar are advantageous.
• the specific holding pressure preferably starts at the value of the specific injection pressure and is then preferably adjusted to decay.
• the tool temperature is preferably in the range 80°C to 140°C, particularly preferably in the range 100 to 130°C.
• process step (1) it further proves to be particularly advantageous and therefore preferred to use a variothermal injection molding process in which the injection molding tool is initially heated to a temperature above the glass transition temperature of the polycarbonate component A), preferably at least 150 ° C, especially preferably at least 160°C is tempered, this temperature is maintained after injecting the polycarbonate composition into the tool for the duration of the holding pressure time and only then is the tool heated to a temperature below the glass transition temperature of the polycarbonate component A), preferably in the range 80 ° C to 140 ° C, especially preferably in the range 100 to 130 ° C, cooled, thereby solidified and finally demolded.
• Such processes can achieve a further improvement in the practical heat resistance of the galvanized components compared to standard injection molding processes.
• the carrier layer (I) produced in process step (1) can in principle be a plate, a profile or a three-dimensional component of any shape. Furthermore, the carrier layer (I) produced in process step (1) can also be a film. Such films suitable as a carrier layer (I) are preferably produced in an extrusion process.
• Carrier layer (I) preferably uses a thermoplastic molding compound containing a branched polycarbonate as component A.
• the carrier layer (I) is preferably temporarily stored until the post-shrinkage process has ended. This usually takes 10 to 48 hours. This intermediate storage further reduces any tensions still in the plastic part.
• a galvano-stable layer preferably a lacquer, which in the later process step (3a) contains the chemical, Electrochemical or physical metal deposition and thus locally prevents galvanization in this area of the plastic carrier in process step (3c).
• the metal layer applied to the plastic carrier surface is partially removed again by mechanical, chemical and/or physical processes, forming openings in the metal layer and locally exposing the plastic carrier surface.
• At least one of the optional process steps (2), (3b) and (4) is used. This results in at least one recess in the preferably multi-layer metal layer on the visible side of the multi-layer body. If the side of the multilayer body facing away from the visible side is also exposed to a metal layer in method step (3), at least one recess also results on this side facing away from the visible side.
• both the visible side and the side of the multilayer body facing away from the visible side are electrochemically exposed to a metal layer in method step (3)
• the by at least one of the optional method steps (2), (3b) and (4) in both Sides of the multilayer body introduced at least one recesses are preferably realized in directly opposite areas of the plastic carrier I.
• the multilayer body Preferably, only the visible side of the multilayer body is provided with a metal layer.
• the plastic carrier from process step (3a-1) is treated with a so-called "conditioner” before process step (3a-2), which acts as a process aid to adsorb the Palladium colloid improved in process step (3a-2).
• a so-called "conditioner” acts as a process aid to adsorb the Palladium colloid improved in process step (3a-2).
• These are substances preferably selected from the group of amines, preferably cyclohexanediamine.
• the “conditioner” is preferably used as an aqueous solution.
• an additional treatment of the plastic carrier can optionally be carried out with an aqueous solution of a Brönstedt acid, preferably a hydrochloric acid solution.
• the extent of palladium adsorption is determined, among other things, by the nature of the palladium colloid and the conditions in the activation step (3a-2), in particular the activation time, the temperature and the concentration of the palladium colloid used.
• the conditions in the activation step (3a-2) and, if necessary, in the preceding conditioning steps as described above are preferably chosen so that an coverage of the plastic carrier surface after process step (3a-3) is at least 4 mg palladium/m 2 , preferably at least 5 mg Palladium/m 2 results.
• the palladium coating deposited after process step (3a-3) is preferably a maximum of 50 mg palladium/m 2 , particularly preferably a maximum of 30 mg palladium/m 2 .
• a closed chemical nickel or chemical copper layer is applied, preferably with a thickness of 500 nm to 5 ⁇ m, particularly preferably 1 ⁇ m to 2 ⁇ m.
• a thin reinforcing layer made of nickel or copper is first electrochemically applied in a first step (3c-2-1) and then a thicker one in a second step (3c-2-2).
• the current density in process step (3c-2-2) is at least 30%, particularly preferably at least 50% higher than the current density in process step (3c-2-1). This preferred embodiment allows the time required to apply the high-gloss copper metal layer to be reduced.
• step (3c-3) the surface appearance of the components according to the invention can be varied in terms of their gloss from high-gloss to matt.
• the components according to the invention are preferably high-gloss, i.e. they have a gloss level of greater than 90, preferably greater than 95, particularly preferably greater than 98 at an viewing angle of 60°.
• the level of gloss is to be understood as the value determined according to ISO 2813 in the 2015 version.
• this carrier layer (I) preferably has a thickness of 0.5 to 5 mm, particularly preferably 1.5 to 3.5 mm, particularly preferably from 1.7 to 3.0 mm.
• This information is to be understood to mean that the carrier layer (I) has a thickness in these areas at every point of its extent, with carrier layer thicknesses of a maximum of 3.0 mm, more preferably a maximum of 2.5 mm, particularly preferred, being preferred in the areas to be illuminated a maximum of 2.2 mm can be used.
• the layer does not necessarily have the same thickness over the entire surface, but can also have different thicknesses, for example due to the formation of reinforcing ribs, due to the shape of the component, due to fastening structures, etc.
• this film preferably has a thickness of 0.1 to 1 mm, more preferably 0.2 to 0.7 mm, particularly preferably 0. 3 to 0.6 mm.
• Such films are suitable for back-injection of the side of the carrier layer (I) facing away from the visible side of the multilayer body with a thermoplastic molding compound with high light transmission.
• the metal layer can be applied to the side of the carrier layer (I) facing the visible side of the multilayer body in an electroplating process as described above both before and after the back-injection of the backing layer film (I), preferably after the back-injection with the thermoplastic molding compound with high light transmission.
• the back-injection layer (III) made of the thermoplastic molding compound with high light transmission preferably has a thickness of 0.5 to 5 mm, particularly preferably 1.5 to 3.5 mm, particularly preferably 1.7 to 3.0 mm, where This information should be understood in the same way as described above.
• thermoplastic molding compounds with high light transmission which are suitable for forming the back-injection layer (III)
• molding compounds which are made from a composition containing aromatic polycarbonate are preferably used.
• the thermoplastic molding compositions suitable for forming the back-injection layer (III) are particularly preferably produced from compositions containing at least one aromatic polycarbonate and at least one representative selected from the group consisting of mold release agents, stabilizers, flow aids, dyes, pigments and additives which increase the light scattering of the polycarbonate .
• the content of mold release agents, stabilizers, flow aids, dyes, pigments and additives, which increase the light scattering of the polycarbonate, in these compositions is preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight. , most preferably 0.2 to 3% by weight.
• the thermoplastic molding material from which the back-injection layer (III) is produced has such a high light transmission that the back-injection layer (III) in its actual thickness has a transmittance of at least one wavelength in the wavelength range of the spectrum from 380 to 780 nm at least 40%, more preferably at least 50%, particularly preferably at least 60% and most preferably at least 70%, the transmittance being determined from the transmission spectrum, which is in accordance with the specifications in DIN/ISO 13468-2 in the version of measured in 2006.
• Component A-1 is a compound having Component A-1:
• Linear polycarbonate based on bisphenol-A with a weight average molecular weight M w of 24,000 g/mol (determined by GPC at room temperature in methylene chloride against a BPA-PC standard).
• Component A-2 is a compound having Component A-2:
• Linear polycarbonate based on bisphenol-A with a weight average molecular weight M w of 28,000 g/mol (determined by GPC at room temperature in methylene chloride against a BPA-PC standard).
• Acrylonitrile (A)-butadiene (B)-styrene (S) polymer produced in the bulk polymerization process, which contains a disperse phase of rubber particles grafted with styrene-acrylonitrile copolymer based on a polybutadiene rubber as a graft base containing styrene enclosed as a separated disperse phase.
• Acrylonitrile copolymer and a styrene-acrylonitrile copolymer matrix that is not chemically bound to the rubber particles and is not enclosed in the rubber particles.
• Component B-1 has an A:B:S ratio of 23:10:67% by weight and a gel content, determined as acetone-insoluble portion, of 20% by weight.
• the acetone-soluble portion of component B-1 has a weight-average molecular weight M w (measured by GPC in tetrahydrofuran as a solvent with polystyrene as a standard) of 165 kg/mol.
• M w weight-average molecular weight measured by GPC in tetrahydrofuran as a solvent with polystyrene as a standard
• the average particle size of the disperse phase D50 measured by ultracentrifugation, is 0.85 ⁇ m.
• the melt flow rate (MVR) of component B-1 measured according to ISO 1133 (2012 version) at 220°C with a ram load of 10 kg, is 6.7 ml/10 min.
• Component B-2 has an A:B:S:BA ratio of 22.5:10:63:4.5% by weight and a gel content, determined as acetone-insoluble portion, of 19% by weight.
• the acetone-soluble portion of component B-2 has a weight-average molecular weight M w (measured by GPC in tetrahydrofuran as a solvent with polystyrene as a standard) of 115 kg/mol.
• the average particle size of the disperse phase D50 measured by ultracentrifugation, is 0.50 ⁇ m.
• the melt flow rate (MFR) of component C-1 measured according to ISO 1133 (2012 version) at 220 ° C with a punch load of 10 kg, is 28 g / 10 min.
• Acrylonitrile-butadiene-styrene graft polymer with a core-shell structure produced by emulsion polymerization of 43% by weight based on the ABS polymer of a mixture of 27% by weight of acrylonitrile and 73% by weight of styrene in the presence of 57% by weight based on the ABS polymer of a particulate cross-linked polybutadiene rubber as a graft base.
• This polybutadiene rubber graft base has a bimodal particle size distribution with maxima at 0.28 ⁇ m and 0.40 ⁇ m and an average particle size D50, measured by ultracentrifugation, of 0.35 ⁇ m.
• Component B-3 does not contain any styrene-acrylonitrile copolymer enclosed in the rubber particles.
• Acrylonitrile-butadiene-styrene graft polymer with a core-shell structure produced by emulsion polymerization of 42% by weight based on the ABS polymer of a mixture of 26% by weight of acrylonitrile and 74% by weight of styrene in the presence of 58% by weight based on the ABS polymer of an agglomerated particulate polybutadiene rubber as a graft base.
• This polybutadiene rubber graft base has a significantly broader and monomodal particle size distribution compared to the graft base used in component B-3. However, the average particle size D50, measured by ultracentrifugation, is in a similar range to that of component B-3 at 0.38 ⁇ m.
• Component B-4 does not contain any styrene-acrylonitrile copolymer included in the rubber particles.
• Styrene-acrylonitrile copolymer produced using the bulk polymerization process, with an acrylonitrile content of 23% by weight and with a weight-average molecular weight M w of 100,000 Da measured by GPC at room temperature in tetrahydrofuran with polystyrene as a standard.
• the molding compounds were produced on a twin-screw extruder ZSK25 from Coperion, Werner & Pfleiderer (Stuttgart, Germany) at a mass temperature of 260 ° C and by applying a negative pressure of 100 mbar (absolute).
• test specimens were produced at a mass temperature of 260°C and at a mold temperature of 80°C on an Arburg 270 E injection molding machine.
• the melt viscosity was determined at a temperature of 260 ° C and a shear rate of 1000 s -1 according to ISO 11443 (version of 2014).
• the IZOD notched impact strength was determined at temperatures ranging from -50°C to 23°C on test bars with dimensions of 80 mm x 10 mm x 4 mm in accordance with ISO 180/1A (2013 version). From the measurements at different temperatures, the tough-brittle transition temperature was determined as the temperature at which 50% of the test specimens in the test break brittle and 50% break tough.
• a puncture test according to ISO 6603-2 (version from 2002) was carried out at -20°C on ten test specimens each with dimensions of 60 mm x 60 mm x 2 mm.
• the percentage of brittle fractures serves as a measure of the material ductility under multiaxial loading.
• a brittle fracture is understood to be a fracture failure in which parts of the test specimen break off in splinters during the puncture test and/or the test specimens show an unstable crack propagation, as a result of which the test specimen breaks apart completely into two parts along such a crack during the test.
• the modulus of elasticity E and the elongation at break were determined on shoulder bars with dimensions of 170 mm x 10 mm x 4 mm at 23 ° C according to ISO 527 (version from 1996) with a strain rate of 1 mm / min (modulus of elasticity) and 5 mm / min, respectively (breaking elongation).
• the softening temperature Vicat B/120 is determined on test rods with dimensions of 80 mm x 10 mm x 4 mm in accordance with ISO 180/1A (version from 2014).
• the total transmittance was determined according to ISO 13468-2 (version from 2006) (light source: D65, observer: 10°) on test specimens with dimensions of 60 mm x 40 mm x 2 mm (i.e. with a material thickness of 2 mm). certainly.
• the half power angle (HPA) of the light intensity was used as a measure of light diffusivity. Larger half-value angles mean greater light scattering.
• the intensity of the light is measured relative to the incident light beam in the range from 0° to 90° after fluoroscopy of a test specimen with dimensions of 60 mm x 40 mm x 2 mm (i.e. with a material thickness of 2 mm) as a function of the polar angle .
• a shaped body was produced from the composition 11 according to the invention, onto which a metal layer could be applied using an electroplating process as described above.
• the data in Table 1 show that the molding compositions according to the invention, which contain component B-1 according to the invention as component B and are in the range according to the invention with regard to the polybutadiene rubber content, have a surprising, advantageous combination of improved light transmission and high light diffusivity (scattering power). Furthermore, the molding compositions according to the invention show an advantageous combination of improved melt flowability (reduced melt viscosity), good mechanical properties, in particular good material toughness even at low temperatures and high heat resistance. However, the molding compositions not according to the invention, which contain as component B the emulsion ABS components B-3 or B-4 not according to the invention or a mass ABS component B-2 not according to the invention, do not fulfill this technical task of the invention. The same applies to the molding compositions from compositions V9 and V13, which lie outside the range according to the invention with regard to their polybutadiene rubber content.

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• 2022
  • 2022-03-16 EP EP22162417.4A patent/EP4245521A1/fr not_active Withdrawn
• 2023
  • 2023-03-09 WO PCT/EP2023/055957 patent/WO2023174781A1/fr unknown

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